The main transition of amorphous polymers is analyzed with respect
to a fine structure by
means of new experimental dynamic shear, dielectric, and heat capacity
data for the following polymers:
poly(n-alkyl methacrylate)s with alkyl = methyl,
ethyl, propyl, butyl, and hexyl, polystyrene,
poly(vinyl
acetate), a series of weakly vulcanized natural rubbers, a series of
butyl rubbers with different carbon
black content, polyisobutylene, and bromobutyl rubber. The
components of the fine structure are assumed
to be a proper glass transition at short times, followed by a confined
flow zone, and, at large times, a
hindering zone caused by entanglements at large times. Two lengths
are assumed to correspond to the
first and third components, respectively, the characteristic length to
the proper glass transition and the
entanglement spacing to the hindering zone. The confined flow will
be described by a dispersion law
(general scaling) across the main transition. The characteristic
length of the glass transition for the
poly(n-alkyl methacrylate)sonly of order 1 nm as
determined by calorimetryis confirmed by backscaling
from the entanglement spacing by means of a Rouse dispersion law for
shear. The fate of the Rouse
modes below the αβ splitting of the glass transition is discussed
for the other amorphous polymers. Finally,
a speculative molecular picture of the different modes in the main
transition is described. The new element
is a low-viscosity longitudinal motion of individual chain parts in the
confined flow zone. A simple
rheological model for the confined flow is also presented.